In-tank toilet dispenser

ABSTRACT

Treatment of water-containing reservoirs with a cleaning composition including a water-dissipatable polyester polymer, the polyester polymer concentration in the reservoir being in an amount effective to capture heavy metal ions, thereby inhibiting staining. In a preferred embodiment, the polyester complexes a perfume, the perfume being released in dilute solution as in the reservoir, whereby a fragrance bloom is provided to the environment.

This is a divisional application of U.S. application Ser. No. 059,352,filed June 8, 1987, now U.S. Pat. No. 4,787,984.

FIELD OF INVENTION

The present invention concerns treatment of water-containing reservoirs,the water therein containing heavy metal ions that may stain thereservoir surfaces. More specifically, the invention concerns treatmentof toilet bowls with a cleaning composition including awater-dissipatable polyester polymer, the polyester polymerconcentration in the bowl water after a flush being in an amounteffective to capture the heavy metal ions in the bowl water, therebyinhibiting staining. In a particularly preferred embodiment of thepresent invention, the polyester polymer contained in the cleaningcomposition complexes a perfume, the perfume being released in dilutesolution as in the bowl, whereby a fragrance bloom is provided to theenvironment and whereby the polyester polymer is available in the bowlwater, having released the sequestered perfume, to capture the heavymetal ions present in the bowl water.

BACKGROUND OF INVENTION

The polyester polymers found to be of utility in the practice of thepresent invention are water-dissipatable polymers such as disclosed inU.S. Pat. No. 4,335,220 to Coney entitled "Sequestering Agents andCompositions Produced Therefrom." According to the Coney patent, certainpolymeric polyesters that comprise the reaction products of (a) at leastone difunctional dicarboxylic acid; (b) at least one difunctionalsulfomonomer containing at least one metal sulfonate group attached toan aromatic nucleus, the functional groups being hydroxy, carboxyl oramino, and (c) a glycol or a glycol and diamine mixture, the diaminehaving two --NRH groups and the glycol containing two --CH₂ OH groups ofwhich at least 0.1 mole percent, based on the total mole percent ofhydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol)having the structural formula H(OCH₂ --CH₂)_(n) OH, n being an integerof 2 and about 500, with the proviso that the mole percent of thepoly(ethylene glycol) within the range is inversely proportional to thequantity of n within the range, said polyester as defined above havingan inherent viscosity of at least about 0.1 as defined in the Coneypatent and including the reaction products based on the ester forming oresteramide derivatives of said reactants (a), (b), and (c), are suitableto sequester finely divided water insoluble, hydrophobic, deformableorganic substances of low dipole moment, i.e., from 0 to 1.8. Examplesof such substances are recited by Coney at column 6, lines 12-21 andinclude sucrose esters, aromatic organic compounds, aliphatic oralicyclic organic compounds, paraffins, vegetable oils, etc. The Coneypatent is incorporated herein by reference.

Kibler et al U.S. Pat. Nos. 3,779,993; 3,734,874 and Sublett U.S. Pat.No. 4,233,196 also each relate to compositions comprising an aqueousdissipation of polymers described as linear, water dissipatable,meltable polyesters or polyesteramides prepared from the reaction ofglycol, dicarboxylic acid, and difunctional monomer components. Each ofthese patents disclose that the difunctional sulfomonomer component ofthe polyesters or polyesteramides therein disclosed may advantageouslybe a dicarboxylic acid or ester thereof containing a metal sulfonategroup, a glycol containing a metal sulfonate group or a hydroxy acidcontaining a metal sulfonate group, the metal ion of the sulfonate saltbeing Na⁺, Li⁺, Mg⁺, Ca⁺⁺, Cu⁺⁺, Ni⁺⁺, Fe⁺⁺, Fe⁺⁺⁺, or the like.

O'Neill et al U.S. Pat. Nos. 4,304,900 and 4,304,901 also each disclosewater-dissipatable polyesters or polyesteramides wherein at least onepart of the monomeric components from which there is derived is apolycarboxylic acid or polyhydric alcohol containing a sulfonic acidsalt moiety derived from a nitrogen containing base, the polymers beinguseful as adhesives, coatings, films and the like.

Small U.S. Pat. No. 4,452,713 ; Callicott U.S. Pat. Nos. 4,374,572,4,302,350, and 4,428,872; Faust et al U.S. Pat. No. 4,087,360; KurtzU.S. Pat. No. 4,283,300; and Rubin U.S. Pat. Nos. 4,049,467 and4,129,423 disclose managanese stain removal/retardation methods andcompositions, suitable for use, for example, in connection with toiletcleaning and automatic dishwashing using an oxidizing agent.

The Callicott, Faust et al and Kurtz patents concern the use ofpolymeric materials, e.g., polyacrylics, partially hydrolyzedpolyacrylamides, sodium polyacrylates, and ethylene-maleic anhydridecopolymers. Small concerns the use of glassy phosphate, while Rubinconcerns the use of dihydroxy maleic acid, dihydroxy tartaric acid, andtheir alkali metal salts.

Goodenough U.S. Pat. No. 3,721,629 discloses a composition and methodfor removing ion stains from porcelain, the composition containing achelate agent able to couple Fe⁺⁺⁺ and a soluble Fe⁺⁺ salt, thecomposition having a pH between 1.5 and 4.5.

SUMMARY OF INVENTION

It is an object of the present invention to provide an in-tank toiletdispenser containing a cleaning composition including awater-dissipatible polyester which inhibits staining of heavy metalions.

Yet another object of the present invention is to sequester a perfumewith the polyester in the composition, said perfume being released tothe atmosphere subsequent to treatment of the reservoir.

These and other objects and advantages will be more readily apparentupon reading the detailed description of the invention, a summary ofwhich follows.

According to the method of the present invention, a water-dissipatiblepolyester polymer which is the reaction product of (a) a difunctionalacid, (b) a difunctional sulfonomer, and (c) a glycol or glycol anddiamine mixture, the polymer having an inherent viscosity (ashereinafter defined) of at least 0.1, preferably above about 0.3, isdispensed into the water-containing reservoir in a concentrationeffective to capture heavy metals contained therein. The polymerconcentration in the reservoir is preferably from about 40 ppb to about100 ppm. The polyester may be incorporated in a cleaning compositioncontaining from about 0.05 to about 8% of the polymer and up to about15% of a surfactant In a particularly preferred embodiment, thecomposition contains a perfume which the polymer sequesters, and whichis released from the polyester in the reservoir and at theconcentrations of the polymer therein. A major portion of the perfume,generally insoluble in water, floats to the surface of the water, and isthen evaporatable, imparting a pleasing fragrance to the atmosphere.

DETAILED DESCRIPTION OF THE INVENTION

Public water supplies as well as private water supplies, for example,water from wells, contain trace levels of various heavy metal ionimpurities, including, for example, Fe⁺⁺⁺, Mn⁺⁺⁺ and Cu⁺⁺. Iron andcopper pipe present in homes and commercial buildings also places heavymetal ions into the water supply. Over time the presence of such ionscauses staining of reservoirs in the home and in commercial buildings,especially porcelain reservoirs such as toilet bowls, urinals, bathtubs,sinks, basins and the like. Typically, from about 0.5 to about 500 ppmof these heavy metal ions in the water supply is sufficient to causestaining.

In one type of cleaner for such reservoirs, an aqueous solution of anactive cleaning constituent or mixture of such constituents, typicallyanionic or nonionic surfactants, is employed. These constituents cleanthe subject reservoir by solubilizing soil deposits. By and large, thistype of cleaning solution is not effective in preventing staining by theoffending heavy metal ions.

Another type of cleaning composition incorporates acids, e.g.,hydrochloric acid, which ionize in solution, and which are effective inremoving and/or preventing staining. Disadvantageously, most surfactantsare not compatible with such acid constituent, and the stain-removingbenefit of the acid cannot be combined with the cleaning power of thesurfactant.

It has been found that certain polyester compounds are useful inretarding staining, when used in cleaning compositions of the firstmentioned type, containing a surfactant or blend of surfactants.

The polyester polymer of the present invention are water-dissipatible,meltable polyesters of the type disclosed in Kibler et al U.S. Pat. Nos.3,779,993 and 3,734,874; Coney U.S. Pat. No. 4,335,220; Sublett U.S.Pat. No. 4,233,196, and O'Neill U.S. Pat. No. 4,304,900 and 4,304,901,all of these patents being incorporated herein by reference thereto.

Accordingly, the reaction product of polymers suitable for use with thepresent invention may be the reaction product of (a) a difunctionaldicarboxylic acid, (b) a difunctional sulfomonomer, and (c) a glycol ora mixture of glycol and diamine, the polymer having an inherentviscosity (as defined in Coney U.S. Pat. No. 4,335,220) of at least 0.1,preferably about 0.3, the term "inherent viscosity" referring toviscosity determinations made at 25° using 0.25 grams of polymer per 100ml. of a solvent composed of 60% by weight phenol and 40% by weighttetrachlorethane.

The difunctional dicarboxylic acid reactant (a) can be aliphatic,alicyclic, and aromatic dicarboxylic acids, for example, succinic,glutaric, adipic, fumaric, maleic, 1,4-cyclohexanedicarboxylic,terephthalic, and phthalic acids. Mixtures of two or more acids can beused. The corresponding anhydrides, esters and acid chlorides of theabove acids are also suitable.

The difunctional sulfomonomer reactant (b) can be a dicarboxylic acid orester containing a metal sulfonate group or a hydroxy acid containing ametal sulfonate group. Preferably, the metal ion is an alkali metal. Thedifunctional sulfomonomer (b) include sulfophthalic, sulfoterephthatic,sulfoisophthalic, and 4-sulfonaphthalene-2,7-dicarboxylic acids, andtheir corresponding esters. Also suitable are metallosulfoarylsulfonates, e.g., 5-sodiosulfoisophthalic acid.

Aliphatic, alicyclic and alkylaryl glycols are suitable as reactant (c)herein, and include ethylene glycol, propylene glycol, p-ethylenediol,1,3-cyclohexanedimethanol and the like. Two or more glycols can be usedin the synthesis of the polyesters suitable herein. Diethylene glycol ispreferred.

The polyester polymers suitable in the compositions of the presentinvention have a molecular weight of from about 10,000 to about 25,000.An example of the aforementioned polyester is the "AQ" polyester series,manufactured by Eastman Chemical Products, Inc., especially AQ 55D,wherein the suffix "D" denotes a dispersion of the polymer. The AQpolymers are available as solid pellets or as aqueous dispersions. Thedispersions typically comprise 20-35% solids, and have viscosities inthe range of 10-50 cps at 100 rpm. Also suitable for use herein are theAQ29 and AQ38 polymers.

It has been found that the polyester polymers herein recite may beincluded within a surfactant containing composition used in the cleaningof reservoirs, especially toilet bowls, to lessen the tendency of di-and trivalent metal ions as may be present in the water supplied to thereservoirs from staining the surfaces thereof, especially porcelainsurfaces. It is critical, however, that the cleaning composition inwhich the polyester is included not contain significant levels ofionizable species, for example, ionizable acids, as the polymers aredestabilized at higher ionic strengths. Preferably, the ionic strengthof the cleaning composition should be less than 0.5 mol/liter. Whendestabilized, the polymer precipitates, making it ineffective for itsintended activity but also possibly preventing proper operation of theautomatic dispenser preferably used to deliver the composition to thereservoir.

The aqueous cleaning composition of the present invention comprises on aweight basis from about 1 to about 15%, preferably from about 2 to about8%, of a nonionic or anionic surfactant and mixtures thereof; from about0.05% to about 10% (active basis), preferably from 0.1 to about 3%, ofthe polyester polymer, and water. While optional, it is quite preferableto include perfume, typically less than about 2%, more specificallybetween 0.05 to 1.0% by weight, of an oil based perfume, and a dye,typically less than 5%, more specifically between 0.25 and 2% by weight.The polymer is provided as a dispersion in the cleaning composition.

It has been further found that perfumes included in the cleaningcomposition are sequestered by the polyester. This is demonstrated bythe low intensity fragrance exhibited by perfume containing compositionsof the present invention, prior to dilution in the reservoir.

Advantageously, when the cleaning composition is diluted, as by use in awater containing reservoir, there is a release or "bloom" of theperfume. While the mechanism is not fully understood, it is believedthat the polymer, when present in aqueous solutions at quite dilutelevels, either unravels to release the perfume or releases the perfumeto preferentially capture the heavy metal ion. Preferably, theconcentration of the polymer in aqueous solution in the reservoirsuitable to obtain release of the perfume is from about 40 parts perbillion to about 100 parts per million, most preferably from about 1 toabout 50 ppm. Importantly, it has been found that dilution of thepolymer as described above does not prevent capture of the offendingheavy metal ions.

Any anionic, nonionic, cationic, amphoteric, or zwitterionic surfactantis suitable in the composition of the present invention, provided thationization is insufficient in the case of the ionizable surfactants tointerfere with the intended function of the polymer. Generally, however,the ionizable surfactants have a low degree of dissociation and,accordingly, do not jeopardize the activity of the polymer. Anionic andnonionic surfactants are especially preferred.

Broadly, the anionic surfactants are water-soluble alkyl or alkylarylcompounds, the alkyl having from about 8 to about 22 carbons, includinga sulfate or sulfonate substituent group that has been base-neutralized,typically to provide an alkali metal, e.g., sodium or potassium, or anammonium anion, including, for example: (1) alkyl and alkylaryl sulfatesand sulfonates having preferably 10 to 18 carbons in the alkyl group,which may be straight or branched chain, e.g., sodium lauryl sulfate andsodium dodecylbenzene sulfonate; (2) alpha-olefin aryl sulfonatespreferably having from about 10 to 18 carbons in the olefin, e.g.,sodium C₁₄₋₁₆ olefin sulfonate, which is a mixture of long-chainsulfonate salts prepared by sulfonation of C₁₄₋₁₆ alpha-olefins andchiefly comprising sodium alkene sulfonates and sodium hydroxyalkanesulfonates; (3) sulfated and sulfonated monoglycerides, especially thosederived from coconut oil fatty acids; (4) sulfate esters of ethoxylatedfatty alcohols having 1-10 mols ethylene oxide, e.g., sodiumpolyoxyethylene (7 mol EO) lauryl ether sulfate, and of ethoxylatedalkyl phenols having 10 mols ethylene oxide and 8 to 12 carbons in thealkyl, e.g., ammonium polyoxyethylene (4 mol EO) nonyl phenyl ethersulfate; (5) base-neutralized esters of fatty acids and isethionic acid,e.g., sodium lauroyl isethionate; (6) fatty acid amides of a methyltauride, e.g., sodium methyl cocoyl taurate, (7) beta-acetoxy- orbeta-acetamido-alkane sulfonates where the alkane has from 8 to 22carbons, and (8) acyl sarcosinates having from 8 to 18 carbons in theacyl, e.g., sodium lauroyl sarcosinate.

The nonionics include (1) fatty alcohol alkoxylates, especially theethoxylates, wherein the alkyl group has from 8 to 22, preferably 12 to18, carbons, and typically 6 to 15 mol alkoxide per molecule, e.g.,coconut alcohol condensed with about nine mols ethylene oxide; (2) fattyacid alkoxylates having from about 6 to about 15 mols alkoxylate,especially the ethoxylate; (3) alkylphenoxy alkoxylates, especially theethoxylates, containing 6 to 12 carbons, preferably octyl or nonyl, inthe alkyl, and having about 5 to 25, preferably 5 to 15 mols alkyleneoxide per molecule, e.g., nonyl phenol ethoxylated with about 9.5 molsethylene oxide (Igepal CO-630); (4) condensates of ethylene oxide with ahydrophobic base formed by condensation of propylene oxide withpropylene glycol, e.g., nonionic surfactants of the Pluronic seriesmanufactured by BASF Wyandotte, (5) condenaates of ethylene oxide withan amine or amide; (6) fatty amine oxides, e.g., stearyl dimethyl amineoxide, and (7) alkylolamides.

Preferred anionics are the alkyl and alkylauryl sulfates and thealpha-olefin aryl sulfonates, while preferred nonionics are the fattyalcohol ethoxylates and the alkyl phenoxy ethoxylates. Preferred dyesare FD&C Blue No.1 (Colour Index No. 42,090), FD&C Green No. 3 (ColourIndex No. 42,053), Acid Blue 249 (Colour Index No. 74220), and ColourIndex No. 52,015.

Typically, the perfume preferably incorporated in the composition of thepresent invention is a mixture of organic compounds admixed so that thecombined odors of the individual components produce a pleasant o desiredfragrance. While perfumes are generally mixtures of various materials,individual compounds may also be used as the perfume ingredient. Theperfume compositions generally contain a main note or the "bouquet" ofthe perfume composition, modifiers which round off and accompany themain note, fixatives including odorous substances that lend a particularnote to the perfume throughout each of the stages of evaporation,substances which retard evaporation, and top notes which are usuallylow-boiling, fresh-smelling materials.

Perfumery raw materials may be divided into three main groups: (1) theessential oils and products isolated from these oils; (2) products ofanimal origin; and (3) synthetic chemicals.

The essential oils consist of complex mixtures of volatile liquid andsolid chemicals found in various parts of plants. Mention may be made ofoils found in flowers, e.g., jasmine, rose, mimosa, and orange blossom;flowers and leaves, e.g., lavender and rosemary; leaves and stems, e.g.,geranium, patchouli, and petitgrain; barks, e.g., cinnamon; woods, e.g.,sandalwood and rosewood; roots, e.g., angelica; rhizomes, e.g., ginger;fruits, e.g., orange, lemon, and gergamot; seeds, e.g., aniseed andnutmeg; and resinous exudations, e.g., myrrh. These essential oilsconsist of a complex mixture of chemicals, the major portion thereofbeing terpenes, including hydrocarbons of the formula (C₅ H₈)_(n) andtheir oxygenated derivatives. Hydrocarbons such as these give rise to alarge number of oxygenated derivatives, e.g., alcohols and their esters,aldehydes and ketones. Some of the more important of these are geraniol,citronellol and terpineol, citral and citronellal, and camphor. Otherconstituents include aliphatic aldehydes and also aromatic compoundsincluding phenols such as eugenol. In some instances, specific compoundsmay be isolated from the essential oils, usually by distillation in acommercially pure state, for example, geraniol and citronellal fromcitronella oil; citral from lemon-grass oil; eugenol from clove oillinalool from rosewood oil; and safrole from sassafras oil. The naturalisolates may also be chemically modified as in the case of citronellalto hydroxy citronellal, citral to ionone, eugenol to vanillin, linaloolto linalyl acetate, and safrol to heliotropin.

Animal products used in perfumes include musk, ambergris, civet andcastoreum, and are generally provided as alcoholic tinctures.

The synthetic chemicals include not only the synthetically made, alsonaturally occurring isolates mentioned above, but also include theirderivatives and compounds unknown in nature, e.g., isoamylsalicylate,amylcinnamic aldehyde, cyclamen aldehyde, heliotropin, ionone,phenylethyl alcohol, terpineol, undecalactone, and gamma nonyl lactone.

Perfume compositions as received from the perfumery house may beprovided as an aqueous or organically solvated composition, and mayinclude as a hydrotrope or emulsifier a surface-active agent, typicallyan anionic or nonionic surfactant, in minor amount. The perfumecompositions are quite usually proprietary blends of many differentfragrance compounds. However, one of ordinary skill in the art, byroutine experimentation, may easily determine whether such a proprietaryperfume blend is suitably sequestered by the polyester in thecompositions of the present invention.

The polyester polymer herein described are dispersible, not soluble, inwater. The polymers are not easily dissipated in cold water, although insome instances cold water is preferred, depending on the particularreactants employed. Typically, dispersions of the polymer are made byadding solid polymer to water heated to about 175 to about 190° F.,accompanied by stirring. The aforementioned Coney, Kibler, et al., andSublett patents describe in greater detail preparation of these polymerdispersions.

A perfume-complexed polyester may be made by subsequently adding theperfume or a perfume solution to the cooled dispersion under conditionsof shear.

It is preferred to admix an aqueous premix of the surfactant to thecooled polymer dispersion or the perfume-complexed polymer dispersion,under conditions of stirring.

When used as a toilet cleaning product, the composition of the presentinvention is preferably dispensed into the toilet tank on the occasionof a flush, the volume of water in the tank being sufficient to achieveadequate dilution to the concentration levels at which the polymerreleases the perfume, for a perfume-complexed polymer. Suitable for usein combination with the subject composition is the dispenser describedin Mack U.S. Pat. No. 3,698,021. Also suitable is the dispenserdisclosed in M. McElfresh U.S. Pat. No. 4,660,231, which is an exampleof a downstroke dispenser and discharges composition as the tank waterlevel drops as a result of a flush. The Mack device is an upstrokedispenser that discharges composition as the tank water level risesduring refilling of the tank, in which case the tank is the primaryreservoir and the entire tank water volume is treated as to remove theoffending ions.

What is claimed is:
 1. An in-tank toilet dispenser containing a cleaningcomposition and adapted to release an effective cleaning amount of saidcomposition into the toilet, said composition comprising up to about 15%surfactant, and from about 0.05 to about 10% by weight of thewater-dissipatable polyester polymer which is the reaction product of(a) a difunctional dicarboxylic acid, (b) a difunctional sulfomonomer,and (c) a glycol or a glycol and diamine mixture, the polyester havingan inherent viscosity of at least 0.1, the cleaning compositioncontaining above about 65% water, the amount of said compositionreleased from the dispenser being sufficient to provide a polymerconcentration of from about 40 ppb to about 100 ppm, whereby heavy metalions are captured by the polymer to inhibit staining.
 2. The dispenserof claim 1 wherein the reactant (a) is selected from the groupconsisting of succinic, glutaric, adipic, fumaric, maleic,1,4-cyclohexanedicarboxylic, phthalic and terephthalic acids; thereactant (b) is selected from the group consisting of sulfophthalic,sulfoterephthalic, sulfoisophthalic and4-sulfonaphthalene-2,7-dicarboxylic acids, and the reactant (c) isselected from the group consisting of ethylene glycol, diethyleneglycol, propylene glycol, p-ethylenediol and 1,3-cyclohexanedimethanol.3. The dispenser of claim 2 wherein the polymer has an inherentviscosity of above about 0.3.
 4. The dispenser composition of claim 2wherein the polymer molecular weight is from about 10,000 to about25,000.
 5. The cleaning composition of claim 1 further comprising aperfume, the perfume being sequestered by said polyester.
 6. Thedispenser of claim 5 wherein the reactant (a) is selected from the groupconsisting of succinic, glutaric, adipic, fumaric, maleic,1,4-cyclohexanedicarboxylic, phthalic and terephthalic acids; thereactant (b) is selected from the group consisting of sulfophthalic,sulfoterephthalic, sulfoisophthalic and4-sulfonaphthanene-2,7-dicarboxylic acids, and the reactant (c) isselected from the group consisting of ethylene glycol, diethyleneglycol, propylene glycol, p-ethylenediol and 1,3-cyclohexanedimethanol.7. The dispenser of claim 6 containing from about 0.1 to 3% polyester,from about 0.05 to about 1.0% perfume, and from about 1% to 8%surfactant.
 8. The dispenser of claim 7 wherein the perfume comprises anessential oil.
 9. The dispenser of claim 7 wherein the perfume comprisesa fragrance constituent selected from the group consisting of geraniol,citronellol, terpineol, citral, citronellal, eugenol, ionone, isobornylacetate, isoamyl salicylate, methyl salicylate, gamma nonyl lactone, andmixtures thereof.